1. Field of the Invention
This invention is related to ethylenically-unsaturated 1,3-diketoamide functional compounds and polymers prepared therefrom. The invention is also related to latex formulations containing polymeric ingredients having 1,3-diketoamide functional pendant moieties which advantageously exhibit excellent hydrolytic stability.
2. Related Background Art
Ethylenically-unsaturated monomers containing active methylene groups such as ##STR1## and polymers prepared from such monomers having pendant active methylene groups have long been known For example, U.S. Pat. No. 3,459,790 discloses acetoacetates, such as 2-acetoacetoxyethyl methacrylate and 2-acetoacetoxyethyl acrylate, for forming polymers to be used as gelatin extenders or substitutes in photographic films.
Polymerizable compounds having amide groups and active methylene crosslinking sites in side chains extending from ethylenically unsaturated backbones are disclosed in U.S. Pat. No. 4,215,195. These polymerizable compounds, which are used to form polymers which can act as polymeric color couplers, binders and gelatin extenders, are generically represented by the formula: ##STR2## wherein R is hydrogen or methyl;
R.sup.1 is cyano or ##STR3## wherein R.sup.2 is alkyl; PA1 Z is --X--R.sup.3 --X-- or ##STR4## wherein each --X-- is --O-- or --NR.sup.4 --, provided at least one --X-- is --NR.sup.4 --, wherein R.sup.4 is hydrogen or alkyl, R.sup.3 is divalent hydrocarbon and D.sub.1 and D.sub.2 together are carbon atoms necessary to complete a 5 to 7 membered ring. Acetoacetamidoethyl methacrylate is exemplified as a useful polymerizable monomer. PA1 A is a group represented by the formula ##STR6## wherein R.sup.1 is hydrogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms; PA1 R.sup.2 is hydrogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms; PA1 X is arylene having 6 to 20 carbon atoms; PA1 R.sup.3 and R.sup.4 are independently hydrogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms; PA1 Y is --NH-- or --O--; PA1 Z is alkylene having 1 to 10 carbon atoms; PA1 m, n and p are independently 0 or 1; and PA1 Q is O or a single bond; and PA1 B is A, an alkyl group having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms. Exemplary arylene radicals include, without limitation, phenylene, naphthylene or the like, which can be substituted or unsubstituted. Preferably X is phenylene and p is 1. PA1 R.sup.2 is hydrogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms; PA1 X is arylene having 6 to 20 carbon atoms; PA1 R.sup.3, R.sup.4 and R.sup.5 are independently hydrogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms; and PA1 R.sup.6 is alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms. Preferably X is phenylene. It is also preferred that R.sup.1 and R.sup.5 are hydrogen, while R.sup.3, R.sup.4 and R.sup.6 are methyl groups. More preferably, R.sup.2 is hydrogen or a methyl group.
The preparation of various acetoacetates and acetoacetamides is well known. For example, J. Witzeman, et al., The Journal of Organic Chemistry, 56, 1713-18 (1991) discloses the preparation of acetoacetates and acetoacetamides by reaction of various nucleophiles with tert-butyl acetoacetates. This reference reports that acetoacetylated materials may be used as chemical intermediates in the pharmaceutical, agrichemical, chemical and polymer industries.
More particularly, it is known to use acetoacetoxy-functional moiety-containing polymers in combination with polyfunctional amines in latex compositions. Such compositions may be applied to substrates to form films by crosslinking the amines with the acetoacetoxy-functional moiety through the formation of enamine linkages. For example, PCT International Publication No. WO 93/16133 (equivalent to U.S. Pat. No. 5,498,659 to Esser) discloses a particularly advantageous storage-stable single-package latex formulation containing a polymeric ingredient having at least acetoacetoxy functional pendant moieties. This reference discloses that preferred acetoacetoxy functional moiety-containing ingredients include acetoacetamides, such as acetoacetamide methacrylate and acetoacetamide acrylate, as well as acetoacetoxyethyl methacrylate ("AAEM"), acetoacetoxyethyl acrylate ("AAEA"), allyl acetoacetate and vinyl acetoacetate. The use of acetoacetamides in a latex formulation is not exemplified. None of these references disclose or suggest an acetoacetamide compound having an arylene radical therein, or the use of such an acetoacetamide in a latex formulation.
U.S. Pat. No. 5,098,974 discloses an acrylic polymer, which is used as a pigment grinding vehicle having pendent tertiary alkyl primary amine groups and at least one other pendent functionality reactive with isocyanate groups. The monomer having pendent tertiary alkyl primary amine groups may be prepared by reacting a tertiary alkyl isocyanate, such as meta-isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate, with a tertiary alcohol, such as diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), in the presence of a catalyst. There is no disclosure or suggestion, however, of preparing acetoacetamides.
While the acetoacetoxy functional moiety-containing ingredients disclosed in WO 93/16133 may be used to provide desirable latex formulations, there is a continuing need for improved hydrolytic stability of acetoacetoxy functional moieties employed in aqueous polymer formulations. A latex formulation having acetoacetoxy functional pendent moieties with improved hydrolytic stability will advantageously have enhanced storage stability and thus significant commercial advantage over prior art formulations.